α-Fe 2 O 3 Tailored Bi 2 WO 6 Hierarchical Microspheres for the Effective Photocatalytic Degradation of Antibiotic Ciprofloxacin and Cationic Rhodamine B Aqueous Dye

α-Fe 2 O 3 Tailored Bi 2 WO 6 Hierarchical Microspheres for the Effective Photocatalytic Degradation of Antibiotic Ciprofloxacin and Cationic Rhodamine B Aqueous Dye | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article α-Fe 2 O 3 Tailored Bi 2 WO 6 Hierarchical Microspheres for the Effective Photocatalytic Degradation of Antibiotic Ciprofloxacin and Cationic Rhodamine B Aqueous Dye Rajkumar P, Jayanthi T. S., Suja R., Vasudeva Reddy Minnam Reddy, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3888631/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract α-Fe 2 O 3 tailored Bi 2 WO 6 hierarchical microspheres have been effectively synthesized and well characterized. The photocatalytic efficacy was improved by the Fe-BW-3% heterojunction on the degradation of ciprofloxacin as a pharmaceutical and rhodamine B as a cationic dye pollutant. The increased photocatalytic activity was attributed to the increment of visible light absorbing ability and reduced rate of light-induced electron and hole recombination by moving electrons from one junction to another. The recycle investigations revealed that the catalysts are stable for CIP and RhB degradation after six cycles. Furthermore, scavenging experiments show that holes were the primary active species for the CIP and RhB degradation. Bi2WO6 α-Fe2O3 Photocatalysis ciprofloxacin Rhodamine B Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Highlights One-step hydrothermal route was adopted to synthesize α-Fe 2 O 3 /Bi 2 WO 6 heterojunction. Redshift in the absorption spectra by the inclusion of α-Fe 2 O 3 promotes the light harvesting ability of the Bi 2 WO 6 . BW-Fe-3% heterojunction exhibits excellent photocatalytic efficiency of 98.09% and 97.37% for CIP and RhB degradation. The plausible photocatalytic degradation mechanism was discussed in detail. 1. Introduction Water is an essential ingredient for sustaining life. The increased use of water in home, agricultural, and industrial sectors has harmed water quality [ 1 ]. Much recent research has revealed that high quantities of emerging pollutants, such as pharmaceutical chemicals, survive in surface waters, soils, and plants. Pharmaceutical compound contamination of water bodies is attributed to two pathways: discharge of medicinal products discharges into water bodies and incorrect discharge of large amounts of medicine left over into the surroundings [ 2 ]. Greater antibiotic dosages in water sources show that contemporary water management methods are not well appropriate for removing antibiotics from water bodies. Hence, there is tremendous concern, because antibiotics are responsible for antibiotic-resistant bacteria and antibiotic-resistant genes, which can disrupt aquatic systems and endanger human health [ 3 ]. As a result, numerous strategies for extracting antibiotics from aqueous media have been developed. Notably, when compared to many conventional and advanced oxidation processes (AOPs), "semiconductor photocatalysis" has been considered a more realistic choice for antibiotic degradation without the usage of any exogenous supply [ 4 – 8 ]. It is a "green" technique in which semiconductor-based photocatalysts absorb photons with energy (eV) larger than their bandgap and form a slew of reactive species superoxide (•O 2 ¯) and hydroxyl (•OH) radicals, and singlet oxygen. TiO 2 has been the maximum preferred semiconductor catalyst for environmental remediation because of its greatest oxidizing power, stability, nontoxicity, and low cost. Nevertheless, TiO 2 's visible light photocatalytic activity is restricted because of its wide range of band gap (3.2 eV). As a result, developing efficient visibly active photocatalysts for pollutant removal is critical [ 9 – 11 ]. Because of its strong oxidation potential, visible-light harvesting ability, and non-toxicity, Bi 2 WO 6 , a layered structure of WO 4 2− and Bi 2 O 2 2+ , demonstrates remarkable photocatalytic properties for the removal of various organic and antibiotic pollutants [ 12 – 17 ]. Bi 2 WO 6 has a low quantum efficiency due to the high rate of light-induced electron-hole recombination between the hybrid orbitals of Bi 6s and O 2p, as well as the empty W 5d orbital [ 18 , 19 ]. As a result, effective solutions for suppressing electron and hole recombination are required. The coupling of Bi 2 WO 6 with a suitable junction has been discovered to be an efficient technique for increasing the efficacy of the photocatalytic activity of the Bi 2 WO 6 photocatalyst by improving the availability of electrons via effective charge separation. The material α-Fe 2 O 3 , as an n-type metal oxide with a moderate energy gap between 2.2–2.4 eV, has been widely researched as a photocatalyst, electrocatalyst, and gas sensor material. Its plentiful raw resources, environmental friendliness, and good conductivity are desirable characteristics for large-scale applications. The unique features of α-Fe 2 O 3 not only increased photocarrier separation and transport but may also result in a higher conduction band level, representing a stronger reduction potential responsible for the formation of reactive species [ 20 , 21 ]. A technique is the combination of α-Fe 2 O 3 and Bi 2 WO 6 semiconductors with appropriate valence (VB) and conduction (CB) band locations favorable for high photocatalytic efficiency. Since, self-assembly of the hierarchical structure constructed with multi nanocrystals as building blocks is an emerging research field in photocatalysis, which provides an available pore wall arrangement and improves electron transport by reducing pressure drop, allowing for more charge carriers to be transferred to the surface of the catalyst, which promotes the improved photoinduced charge separation. Herein, we report the synthesis of α-Fe 2 O 3 tailored Bi 2 WO 6 hierarchical microsphere via a simple hydrothermal approach. The α-Fe 2 O 3 /Bi 2 WO 6 heterojunction has significantly improved photocatalytic performance in the removal of ciprofloxacin (CIP) rhodamine B (RhB) within a tailoring dosage of α-Fe 2 O 3 (1–4%), with Fe-3% exhibiting the best photocatalytic reaction kinetics. The UV-Vis DRS spectra of the heterojunction exhibit an effective redshift from 470 to 550 nm with increasing the modification content of α-Fe 2 O 3 . The photocatalytic mechanism of improved activity was studied and proposed using PL spectra and predicted valence and conduction band positions. 2. Materials and Methods 2.1 Chemical and Reagents Bismuth nitrate pentahydrate (Bi(NO 3 ) 3 .5H 2 O), sodium tungstate dehydrate (Na 2 WO 4 .2H 2 O), ferric chloride hexahydrate (FeCl 3 .6H 2 O), sodium hydroxide (NaOH), nitric acid (HNO 3 ), RhB (C 28 H 31 C l N 2 O, C.I. 45170) and ciprofloxacin (C 17 H 18 FN 3 O 3 ) were bought from Sigma-Aldrich, Pvt. Ltd. India. All the materials were of analytical grade (AR) and were utilized further in any purification. Every single experiment was conducted using double-distilled (DD) water. 2.2. Synthesis of α-Fe 2 O 3 -Bi 2 WO 6 hierarchical microsphere The hydrothermal process was used to synthesize α-Fe 2 O 3 anchored Bi 2 WO 6 heterojunction without the aid of any surfactants. Typically, aqueous solutions of FeCl 3 .6H 2 O and NaOH were mixed together to obtain the precipitate of Fe(OH) 3 . The attained product was washed multiple times with DD water and sonicated for 10 min to disperse completely. Then the optimum concentrations of Bi(NO 3 ) 3 .5H 2 O were added in 30 mL of 1.5 M HNO 3 and sodium tungstate salt was added in 30 mL of distilled water, separately, and mixed with continuous stirring to obtain suspension with white color. After that, different percentages (1, 2, 3, and 4%) of Fe 2 O 3 were added whilst being constantly stirred to create the dark red suspension. The resulting mixture was transferred to the 100 mL of Teflon-lined autoclave and the reaction mixture was heated at 160°C for 12 hours. After the autoclave was cooled down to room temperature, the obtained heterojunction powder was collected by centrifugation and washed multiple times with DD water followed by 99% ethanol by centrifugation method and then dried at 70°C. Finally, the obtained α-Fe 2 O 3 -Bi 2 WO 6 heterojunction with different Fe concentration was labeled as Fe-BW-0%, Fe-BW-1%, Fe-BW-2%, Fe-BW-3% and Fe-BW-4%. 2.3. Characterizations The powder X-ray diffraction (XRD, PANalytical) method was carried out (Rigaku D/max-RB equipment with Cu K radiation) to examine the purity and crystal structure of the synthesized catalysts. To analyze the morphological structure of the heterojunction, field emission scanning electron microscopy (FE-SEM: JEOL, JSM-5910) followed by transmission electron microscopy (HR-TEM: JEM-2011F, JEOL, Japan) was used. For elemental characterization of the α-Fe 2 O 3 -Bi 2 WO 6 heterojunction, EDX (EX-2300BU, Jeol) spectroscopic analysis was performed. The elemental mixture and chemical states of the synthesized catalyst were examined using high-resolution X-ray photoelectron spectroscopy (HR-XPS: Leybold-Heraeus LHS-10 spectrometer). A fluorescence spectrophotometer (RF- 5300PC, Shimadzu, Japan) was used to measure the photoluminescence (PL). A UV-visible spectrophotometer equipped with diffused reflectance spectra (Shimadzu UV-2450) was used to examine the absorption spectra of the catalyst. 2.4. Photocatalytic degradation experiment The photocatalytic activities of all as-prepared photocatalysts were tested by observing the degradation of antibiotic ciprofloxacin and cationic RhB aqueous pollutants when exposed to visible light. A 300 W Xe arc lamp was employed as the light energy source. The following procedure was conducted at room temperature: 20 mg of all synthesized photocatalysts were added separately to 100 mL of 10 ppm ciprofloxacin and rhodamine B aqueous solution. Prior to illumination, the catalyst was dispersed by stirring the suspensions for 30 minutes in the dark. At regular time intervals, 4 mL of the sample was out and the supernatant was collected by centrifugation. The concentration of Ciprofloxacin and RhB aqueous pollutants was determined by determining the absorbance using a UV-Vis spectrophotometer (Shimadzu UV-2450) at maximum absorption of λ max at 276 and 554 nm, respectively. 3. Results and Discussion 3.1. Characterizations of synthesized catalysts The crystalline structure and purity of Bi 2 WO 6 and α-Fe 2 O 3 /Bi 2 WO 6 composites were determined using a typical XRD technique. As shown in Fig. 1 a, eight distinctive diffraction peaks of pure Bi 2 WO 6 at 2 theta = 28.1, 32.5, 46.4, 56.7, 59.4, 69.4, 76.3, and 78.9° were indexed to the (131), (200), (202), (133), (262), (400), (333), and (204), reflections, indicating that the pure-phase Bi 2 WO 6 is an orthorhombic structure with the JCPDS Card No. of 79-2381 [ 22 – 25 ]. According to Fig. 1 b, as the Fe/Bi molar ratio was amplified from 1 to 4, the intensity of the diffraction planes matching to the (1 1 0) of α-Fe 2 O 3 (JCPDS 33–0664) steadily rose, implying that the α-Fe 2 O 3 was formed in the α-Fe 2 O 3 /Bi 2 WO 6 heterojunction [ 26 , 27 ]. In the patterns, no recognizable peaks of any impurity were found. As a result, the hierarchically structured composite comprises Bi 2 WO 6 and α-Fe 2 O 3 . Figure 2 (a and b) SEM images of Bi 2 WO 6 , (c) lattice fringes of Fe-BW-3%, mapping analysis images of (d) mixed, (e) Bi, (f) W, (g) O and (h) Fe, (i) EDAX spectrum of Fe-BW-3% catalyst. Figure 2 shows SEM and HR-TEM images of the Fe-BW-3 catalyst. The SEM image in Fig. 2 a indicates that the Fe-BW-3 catalyst is a homogenous, sphere-like hierarchically built structure ranging in diameter from 2 to 5 um. The microsphere was generated by self-assembling and Ostwald ripening smooth nanoplates. Because of the vast number of pores in the overlapping nanosheets, Bi 2 WO 6 can be employed as a transmission mechanism for tiny molecules. It aided the reactant and product molecules by moving into and out of the substance and facilitating chemical reactions. The interplanar spacing computed from the lattice fringes was 209 nm, which corresponds to the (131) plane of the orthorhombic Bi 2 WO 6 structure. Furthermore, elemental mapping and EDS were employed to evaluate the Fe-BW-3% catalyst; the results proved the presence of the components Bi, W, Fe, and O, as shown in Fig. 2 i [ 28 ]. As shown in Fig. 2 d-h, the elemental mapping images demonstrated that Bi, W, Fe, and O were spread uniformly. The presence and chemical state of the elements in the α-Fe 2 O 3 /Bi 2 WO 6 heterojunction were analyzed through high-resolution HR-XPS spectra. The doublet signals correspond to the Bi 4f 5/2 and 4f 3/2 signals were perceived at binding energies (BE) of 164.4 eV and 159.1 eV, respectively, which could be allocated to the Bi 3+ species in the sample (Fig. 3 a) [ 29 ]. The W 4f 7/2 and 4f 5/2 were consigned two distinctive signals in the W 4f spectra at 37.54 eV and 35.36 eV, respectively (Fig. 3 b)[ 30 ]. The signal at 725 eV belonged to Fe 2p 1/2 , as shown in Fig. 3 c, indicating the existence of Fe 3+ . Also, the O 1s core level spectra exhibited a significant signal at 530.1 eV, which corresponds to lattice oxygen. The XPS examination results show the creation of α-Fe 2 O 3 in the α-Fe 2 O 3 /Bi 2 WO 6 heterojunction, which is consistent with the powder XRD analysis. Figure 4 a depicts the UV-visible diffuse reflection spectra (DRS) of Bi 2 WO 6 , Fe-BW-1%, Fe-BW-2%, Fe-BW-3%, and Fe-BW-1%. Bi 2 WO 6 exhibits absorption in the UV to visible region with a shorter wavelength than 460 nm. The spectrum's crisp shape suggests that the visible-light absorption was generated by the band-gap transition instead of the transition from the impure conduct level. The optical absorption of α-Fe 2 O 3 /Bi 2 WO 6 composite exhibits a significant shift towards higher wavelength and enhanced absorbance in the visible-light region when compared to pure Bi 2 WO 6 , which can be attributed to the communal photosensitization of Bi 2 WO 6 and α-Fe 2 O 3 . Furthermore, the increased loading of α-Fe 2 O 3 in the composite appears to improve visible light absorption. It demonstrates that modifying α-Fe 2 O 3 can effectively extend the visible-light responsiveness of Bi 2 WO 6 , which is advantageous to using direct sunlight energy for the degradation of pollutants. The photoluminescence (PL) spectra of the catalyst resulting from the rate of the electron-hole recombination can be utilized to reveal the electron movement, transfer, and recombination mechanisms of photoinduced electrons with holes [ 31 ]. The reduced PL intensity frequently suggests a reduced recombination rate and, as a result, enhanced photocatalytic activity. Figure 4 b depicts recorded PL spectra of bare Bi 2 WO 6 and α-Fe 2 O 3 /Bi 2 WO 6 heterojunction stimulated at 320 nm with varying Fe percentages, which also had the same broad emission in the 400–550 nm range. However, the PL intensities of the heterojunction catalysts are reduced, indicating that a heterojunction effect has been produced between α-Fe 2 O 3 and Bi 2 WO 6 . The composite containing Fe-3% had the smallest PL emission, indicating the greatest hindrance to photogenerated carrier recombination. However, the PL emission of heterojunction with Fe-4% increases when compared to composite with Fe-3%. Under light illumination, the BW-Fe-3% catalysts were found to have higher activity in the removal of antibiotic ciprofloxacin and cationic rhodamine B aqueous dye. Figure 4 UV-Vis DRS and photoluminescence spectra of Fe-BW-0%, Fe-BW-1%, Fe-BW-2%, Fe-BW-3% and Fe-BW-4% catalysts 3.2 Photocatalytic degradation activity Ciprofloxacin and rhodamine B were chosen as pharmaceutical and cationic dye pollutants to assess the photocatalytic capacity of all synthesized photocatalysts. The CIP and RhB degradation efficiency for all synthesized materials studied and shown in Figs. 5 a-d and 6 a-d was calculated, as was the seeming rate constant (k) based on a pseudo-first-order kinetic technique. In the absence of a photocatalyst, the degradation efficiency was minimal in the dark reaction, indicating that the CIP (1.97%) and RhB (2.3%) were primarily degraded by catalyst photo-absorption. In addition, the dark test was conducted for the adsorption of pollutants (CIP and RhB) removal, with the percentages being 13.33 and 21.68%, respectively (Fig. 5 b and 6 b). Pristine Bi 2 WO 6 demonstrated minimal photocatalytic activity for CIP (42.4%) and RhB (56.8%) after 180 min. of visible light irradiation. CIP and RhB removal effectiveness was significantly improved over α-Fe 2 O 3 /Bi 2 WO 6 heterojunction and the corresponding absorption plots were presented in Figs. 5 a and 6 a. Among all samples, the BW-Fe-3% catalyst demonstrated the highest photocatalytic efficiency of 98.09% and 97.37% for CIP and RhB degradation, respectively. CIP and RhB degradation percentages for BW-Fe-1%, BW-Fe-2%, and BW-Fe-4% were calculated to be 49.71 and 68.8%, 70.35 and 76.84%, and 88.67 and 88.25%, respectively. The kinetic model (k= -ln(C t /C 0 )) was utilized to evaluate the dye removal kinetics, as shown in Figs. 5 d and 6 d. The kinetic values of CIP degradation for BW, BW-Fe-1%, BW-Fe-2%, BW-Fe-3%, and BW-Fe-4%, respectively, were estimated to be 0.00329, 0.0054, 0.00259, 0.01843, and 0.01066 min − 1 , respectively. Also, the kinetic values of 0.0066, 0.00448, 0.00761, 0.01953, and 0.01169 min − 1 were obtained for RhB degradation using BW, BW-Fe-1%, BW-Fe-2%, BW-Fe-3%, and BW-Fe-4% catalysts. The increased photocatalytic degradation efficiency is principally owing to the considerable amount of visible light harvested and the decreased rate of photoinduced electron-hole recombination caused by α-Fe 2 O 3 -tailored Bi 2 WO 6 heterojunction formation. The peak shift for RhB deterioration has been observed towards the lower wavelength. RhB is well known for its capability to harvest visible light (480–580 nm) range due to the dye's ground and excited states. The energy potential of the conduction band of Bi 2 WO 6 is negative than the lowest empty molecular orbit of RhB. As a result, the photosensitized process, which involves transferring an excited electron from RhB to Bi2WO6's conduction band, is thermodynamically possible. The blue shift has been identified as a stepwise N-de-ethylation of RhB caused by photosensitization. According to the findings, RhB degradation is caused by the interaction of band cleavage degradation of connected structures and photosensitized N-de-ethylation processes. Figure 5 (a) Absorption spectra of CIP degradation over Fe-BW-3% catalyst, % of degradation, C t /C 0 and –ln(C t /C 0 ) for Fe-BW-0%, Fe-BW-1%, Fe-BW-2%, Fe-BW-3% and Fe-BW-4% catalysts The recycling experiments in the light-irradiated photocatalytic degradation of both CIP and RhB were tested to assess the stability of the best-performing (BW-Fe-3%) photocatalyst, which is a significant consideration in practical use. The photocatalyst does not show the apparent loss in photocatalytic degradation of both CIP and RhB after six repeated cycles, as illustrated in Fig. 7 a. BW-Fe-3% composite is thought to have potential applications for lowering water pollutants due to its outstanding photocatalytic performance and good reusability. Figure 6 (a) Absorption spectra of RhB degradation over Fe-BW-3% catalyst, % of degradation, C t /C 0 and –ln(C t /C 0 ) for Fe-BW-0%, Fe-BW-1%, Fe-BW-2%, Fe-BW-3% and Fe-BW-4% catalysts 3.3. Photocatalytic degradation mechanism Scavenging experiments were carried out prior to the mechanism to recognize the primary reactive species for the degradation of CIP and RhB [ 32 , 33 ]. IPA was utilized as a •OH scavenger, KI as a h + radicals scavenger, CCl 4 as an electron scavenger, and BQ as a superoxide radicals scavenger. For CIP photodegradation, superoxide, electrons, hydroxyl, and holes group degradation rates were 10.34, 6.43, 40.63, and 69.43%, respectively. Similarly, RhB degradation studies with superoxide, electrons, hydroxyl, and hole groups were carried out, and the percentages obtained were 7.53, 3.53, 30.43, and 74.55%, respectively. The results indicated that the addition of BQ and CCl 4 to the reaction had no significant effect. This revealed that the principal active species in the photocatalytic reaction were not free electrons and •O 2− radicals. The reaction was greatly hindered when KI was introduced, representing that the primary reactive species were holes and hydroxyl radicals were identified as the secondary active radicals. Theoretical prediction using absolute electronegativity is an efficacious method for determining the band edge of oxide photocatalysts. The following calculation can be used to compute a semiconductor's valence and conduction band edge at zero charge[ 34 – 36 ]: $${E}_{CB}=X-{E}_{0}-0.5{E}_{g}$$ $${E}_{VB}={E}_{CB}+{E}_{g}$$ Where X denotes the electronegativity of a metal oxide, given as the mean values of presented atoms in the catalysts; E c denotes the energy of free electrons related to the hydrogen scale (about 4.5 eV); E g denotes the semiconductor's energy bandgap. Based on the calculated E g of Bi 2 WO 6 in UV-Vis absorption. The CB and VB locations of Bi 2 WO 6 are both more anodic than α-Fe 2 O 3 catalyst. As a result, the band-gap potential difference would cause irreversible carrier transfer at the α-Fe 2 O 3 /Bi 2 WO 6 interface. Figure 8 Probable photocatalytic mechanism for the removal of CIP and RhB over α-Fe 2 O 3 tailored Bi 2 WO 6 heterojunction. As shown in Fig. 8 , under Xe lamp irradiation, Bi 2 WO 6 and α-Fe 2 O 3 can be concurrently induced to excite electrons from the VB to the CB and holes left in the semiconductor valence band. Following that the e¯ from the CB of α-Fe 2 O 3 would be swiftly transferred to the conduction band of Bi 2 WO 6 , while h + from the VB of Bi 2 WO 6 may be transported to that of α-Fe 2 O 3 . Therefore, the photoinduced electrons and holes are effectually segregated at the α-Fe 2 O 3 /Bi 2 WO 6 interface before migrating to the surfaces of structures to be involved in the photocatalytic degradation process. The enhanced photocatalytic activity for CIP photodegradation can be ascribed to the synergy effect of α-Fe 2 O 3 and Bi 2 WO 6 . With the photocatalytic and photosensitized processes collaborate to degrade RhB dye. Rhodamine b can absorb incident light flux due to the intermolecular transition, in addition to the energy bandgap coupling of semiconductors. The excited state photoelectrons can be directly transferred into the CB of Bi 2 WO 6 and subsequently caught by O 2 to initiate further processes for dye mineralization. As a result, the α-Fe 2 O 3 /Bi 2 WO 6 composite has improved photodegradation efficacy for both dye and antibiotic contaminants. 4. Conclusion The hierarchically α-Fe 2 O 3 /Bi 2 WO 6 heterojunction was effectively synthesized in a facile hydrothermal technique and characterized well. The diffused reflectance spectroscopy of the α-Fe 2 O 3 /Bi 2 WO 6 heterojunction revealed a red shift when compared to bare Bi 2 WO 6 . The photocatalytic performance of the BW-Fe heterojunction photocatalyst in the removal of CIP and RhB aqueous pollutants under light illumination was significantly greater than that of pristine Bi 2 WO 6 . The improved photocatalytic performance of the α-Fe 2 O 3 /Bi 2 WO 6 composite can be ascribed to its hierarchical enhanced photo absorption and effective charge carrier separation. After six reaction cycles, the heterojunction catalyst still showed strong photocatalytic activity for both CIP and RhB degradation. Thus, the combination of Bi 2 WO 6 and α-Fe 2 O 3 will be attractive since it may exist as a means to endorse the charge separation of photoinduced electrons and holes and boost photocatalytic efficiencies for the removal of antibiotic and cationic dye pollutants. Declarations Conflict of Interest statement: This research did not involve human or animal samples. Data Availability Statement: Applicable based on request Acknowledgement: Dr. Mohd Afzal extends his appreciation to Researchers Supporting Project number (RSPD2024R979), King Saud University, Riyadh, Saudi Arabia, for financial assistance. Statements & Declarations We confirm that the manuscript has been read and approved by all named authors and that there are no other persons who satisfied the criteria for authorship but are not listed. 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B, Environ. 140–141 (2013) 299–305. https://doi.org/10.1016/j.apcatb.2013.04.014 . C. Huang, L. Chen, H. Li, Y. Mu, Z. Yang, Synthesis and application of Bi2WO6 for the photocatalytic degradation of two typical fluoroquinolones under visible light irradiation, RSC Adv. 9 (2019) 27768–27779. https://doi.org/10.1039/c9ra04445k . X.F. Cao, L. Zhang, X.T. Chen, Z.L. Xue, Microwave-assisted solution-phase preparation of flower-like Bi 2WO6 and its visible-light-driven photocatalytic properties, CrystEngComm. 13 (2011) 306–311. https://doi.org/10.1039/c0ce00031k . M. Qayoom, K.A. Shah, A.H. Pandit, A. Firdous, G.N. Dar, Dielectric and electrical studies on iron oxide (α-Fe2O3) nanoparticles synthesized by modified solution combustion reaction for microwave applications, J. Electroceramics. 45 (2020) 7–14. https://doi.org/10.1007/s10832-020-00219-2 . C. Jaramillo-Páez, J.A. Navío, M.C. Hidalgo, A. Bouziani, M. El Azzouzi, Mixed α-Fe2O3/Bi2WO6 oxides for photoassisted hetero-Fenton degradation of Methyl Orange and Phenol, J. Photochem. Photobiol. A Chem. 332 (2017) 521–533. https://doi.org/10.1016/j.jphotochem.2016.09.031 . S. Mosleh, K. Dashtian, M. Ghaedi, M. Amiri, A Bi2WO6/Ag2S/ZnS: Z-scheme heterojunction photocatalyst with enhanced visible-light photoactivity towards the degradation of multiple dye pollutants, RSC Adv. 9 (2019) 30100–30111. https://doi.org/10.1039/c9ra05372g . M. Liu, X. Xue, S. Yu, X. Wang, X. Hu, H. Tian, H. Chen, W. Zheng, Improving Photocatalytic Performance from Bi2WO6@MoS2/graphene Hybrids via Gradual Charge Transferred Pathway, Sci. Rep. 7 (2017) 1–11. https://doi.org/10.1038/s41598-017-03911-6 . R. Tang, H. Su, Y. Sun, X. Zhang, L. Li, C. Liu, B. Wang, S. Zeng, D. Sun, Facile Fabrication of Bi2WO6/Ag2S Heterostructure with Enhanced Visible-Light-Driven Photocatalytic Performances, Nanoscale Res. Lett. 11 (2016). https://doi.org/10.1186/s11671-016-1319-7 . Y. Geng, P. Zhang, S. Kuang, Fabrication and enhanced visible-light photocatalytic activities of BiVO4/Bi2WO6 composites, (2014) 46054–46059. https://doi.org/10.1039/C4RA07427K . F. Ma, Q. Yang, Z. Wang, Y. Liu, J. Xin, J. Zhang, Y. Hao, L. Li, Enhanced visible-light photocatalytic activity and photostability of Ag3PO4/Bi2WO6 heterostructures toward organic pollutant degradation and plasmonic Z-scheme mechanism, RSC Adv. 8 (2018) 15853–15862. https://doi.org/10.1039/c8ra01477a . D. Ma, J. Wu, M. Gao, Y. Xin, T. Ma, Y. Sun, Fabrication of Z-scheme g-C3N4/RGO/Bi2WO6 photocatalyst with enhanced visible-light photocatalytic activity, Chem. Eng. J. 290 (2016) 136–146. https://doi.org/10.1016/j.cej.2016.01.031 . F. Ren, J. Zhang, Y. Wang, Enhanced photocatalytic activities of Bi2WO6 by introducing Zn to replace Bi lattice sites: A first-principles study, RSC Adv. 5 (2015) 29058–29065. https://doi.org/10.1039/c5ra02735g . K. Jothivenkatachalam, A. Seetharaman, A. Eftekhari, S. Dillibabu, A. Nithya, M. Kandasamy, M. Gopalan, N. Maheswari, D. Sivasubramanian, Ni-Doped SnO 2 Nanoparticles for Sensing and Photocatalysis, ACS Appl. Nano Mater. 1 (2018) 5823–5836. https://doi.org/10.1021/acsanm.8b01473 . X. Liu, Q. Lu, J. Liu, Electrospinning preparation of one-dimensional ZnO/Bi2WO6 heterostructured sub-microbelts with excellent photocatalytic performance, J. Alloys Compd. 662 (2016) 598–606. https://doi.org/10.1016/j.jallcom.2015.12.050 . Additional Declarations No competing interests reported. Supplementary Files floatimage1.jpeg Graphical Abstract Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-3888631","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":269774431,"identity":"d60c7982-79fc-4767-857b-c9f3a1e0e7c1","order_by":0,"name":"Rajkumar P","email":"","orcid":"","institution":"Er. Perumal Manimekalai College of Engineering","correspondingAuthor":false,"prefix":"","firstName":"Rajkumar","middleName":"","lastName":"P","suffix":""},{"id":269774432,"identity":"ad815ca6-4209-40a4-83d4-b57504517798","order_by":1,"name":"Jayanthi T. S.","email":"","orcid":"","institution":"Vivekananda College","correspondingAuthor":false,"prefix":"","firstName":"Jayanthi","middleName":"T.","lastName":"S.","suffix":""},{"id":269774433,"identity":"7ca57987-6723-449b-b8eb-e6123ca7badf","order_by":2,"name":"Suja R.","email":"data:image/png;base64,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","orcid":"","institution":"Thiru. A. Govindasamy government Arts college","correspondingAuthor":true,"prefix":"","firstName":"Suja","middleName":"","lastName":"R.","suffix":""},{"id":269774434,"identity":"fc5827f7-6f70-4598-8fc1-aa3e1ef9612e","order_by":3,"name":"Vasudeva Reddy Minnam Reddy","email":"","orcid":"","institution":"Yeungnam University","correspondingAuthor":false,"prefix":"","firstName":"Vasudeva","middleName":"Reddy Minnam","lastName":"Reddy","suffix":""},{"id":269774435,"identity":"00b8958f-f12a-4e9e-b40c-9836b5c1394a","order_by":4,"name":"Woo Kyoung Kim","email":"","orcid":"","institution":"Yeungnam University","correspondingAuthor":false,"prefix":"","firstName":"Woo","middleName":"Kyoung","lastName":"Kim","suffix":""},{"id":269774436,"identity":"e900df71-69ce-4e9d-82af-2a6360b3ea2e","order_by":5,"name":"Afzal Mohd","email":"","orcid":"","institution":"King Saud University","correspondingAuthor":false,"prefix":"","firstName":"Afzal","middleName":"","lastName":"Mohd","suffix":""}],"badges":[],"createdAt":"2024-01-22 17:46:31","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3888631/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3888631/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":50317718,"identity":"e6399c25-4d83-4f6f-a4a5-fc6253e41084","added_by":"auto","created_at":"2024-01-29 16:27:34","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":62557,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Powder XRD patterns of Fe-BW-0%, Fe-BW-1%, Fe-BW-2%, Fe-BW-3%, and Fe-BW-4% catalysts and (b) enlarged view of (131) plane of α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e.\u003c/p\u003e","description":"","filename":"F1.png","url":"https://assets-eu.researchsquare.com/files/rs-3888631/v1/a0b01d88f557cbcd2b45948f.png"},{"id":50318546,"identity":"72b66c30-23cb-404c-b946-23d4767e926a","added_by":"auto","created_at":"2024-01-29 16:35:35","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":417737,"visible":true,"origin":"","legend":"\u003cp\u003e(a and b) SEM images of Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e, (c) lattice fringes of Fe-BW-3%, mapping analysis images of (d) mixed, (e) Bi, (f) W, (g) O and (h) Fe, (i) EDAX spectrum of Fe-BW-3% catalyst.\u003c/p\u003e","description":"","filename":"F2.png","url":"https://assets-eu.researchsquare.com/files/rs-3888631/v1/fff0bea7e8a8b1c31f33ac53.png"},{"id":50317719,"identity":"f02c1149-a999-44fe-84ef-1048b4e20e99","added_by":"auto","created_at":"2024-01-29 16:27:35","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":121209,"visible":true,"origin":"","legend":"\u003cp\u003eHR-XPX spectra of (a) Bi 4f, (b) W 4f, (c) Fe 2p and (d) O 1s for of Fe-BW-3% catalyst\u003c/p\u003e","description":"","filename":"F3.png","url":"https://assets-eu.researchsquare.com/files/rs-3888631/v1/46ed63447b8d7b538c3de80c.png"},{"id":50318547,"identity":"1e9b52ce-7084-4972-8c4c-1afcb3c5858c","added_by":"auto","created_at":"2024-01-29 16:35:35","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":190937,"visible":true,"origin":"","legend":"\u003cp\u003eUV-Vis DRS and photoluminescence spectra of Fe-BW-0%, Fe-BW-1%, Fe-BW-2%, Fe-BW-3% and Fe-BW-4% catalysts\u003c/p\u003e","description":"","filename":"F4.png","url":"https://assets-eu.researchsquare.com/files/rs-3888631/v1/abd6b1f0dd21cc6824158668.png"},{"id":50317724,"identity":"41cfaaee-9bae-4da8-87a2-6c12790fe8ea","added_by":"auto","created_at":"2024-01-29 16:27:35","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":145967,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Absorption spectra of CIP degradation over Fe-BW-3% catalyst, % of degradation, C\u003csub\u003et\u003c/sub\u003e/C\u003csub\u003e0\u003c/sub\u003e and –ln(C\u003csub\u003et\u003c/sub\u003e/C\u003csub\u003e0\u003c/sub\u003e) for Fe-BW-0%, Fe-BW-1%, Fe-BW-2%, Fe-BW-3% and Fe-BW-4% catalysts\u003c/p\u003e","description":"","filename":"F5.png","url":"https://assets-eu.researchsquare.com/files/rs-3888631/v1/e6fca55ca46badae7cd367c2.png"},{"id":50317720,"identity":"8b038b06-5e77-4cff-b4a0-efaed3cdd928","added_by":"auto","created_at":"2024-01-29 16:27:35","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":138544,"visible":true,"origin":"","legend":"\u003cp\u003e(a) Absorption spectra of RhB degradation over Fe-BW-3% catalyst, % of degradation, C\u003csub\u003et\u003c/sub\u003e/C\u003csub\u003e0\u003c/sub\u003e and –ln(C\u003csub\u003et\u003c/sub\u003e/C\u003csub\u003e0\u003c/sub\u003e) for Fe-BW-0%, Fe-BW-1%, Fe-BW-2%, Fe-BW-3% and Fe-BW-4% catalysts\u003c/p\u003e","description":"","filename":"F6.png","url":"https://assets-eu.researchsquare.com/files/rs-3888631/v1/470f922744239e9024ba3990.png"},{"id":50317727,"identity":"7cc60e45-7df9-4104-8837-582d005d3253","added_by":"auto","created_at":"2024-01-29 16:27:35","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":158621,"visible":true,"origin":"","legend":"\u003cp\u003eRecycle and scavenging experiments on CIP and RhB degradation over best best-performed Fe-BW-3% catalyst\u003c/p\u003e","description":"","filename":"F7.png","url":"https://assets-eu.researchsquare.com/files/rs-3888631/v1/2e7424c68406efde778ec73b.png"},{"id":50317726,"identity":"114e9b47-3317-438f-a659-9744607487c1","added_by":"auto","created_at":"2024-01-29 16:27:35","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":85782,"visible":true,"origin":"","legend":"\u003cp\u003eProbable photocatalytic mechanism for the removal of CIP and RhB over α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e tailored Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003eheterojunction.\u003c/p\u003e","description":"","filename":"F8.png","url":"https://assets-eu.researchsquare.com/files/rs-3888631/v1/0a978865597e6986d7f543d0.png"},{"id":50824249,"identity":"00410d9c-b19f-4dd6-bdb2-d2c53e81f7a3","added_by":"auto","created_at":"2024-02-07 22:55:05","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1641349,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3888631/v1/994722a6-4aec-4fc7-a3db-a1d845dc62fc.pdf"},{"id":50317721,"identity":"60589041-c7aa-4559-9bba-806a13f33a99","added_by":"auto","created_at":"2024-01-29 16:27:35","extension":"jpeg","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":400835,"visible":true,"origin":"","legend":"\u003cp\u003eGraphical Abstract\u003c/p\u003e","description":"","filename":"floatimage1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-3888631/v1/d1f1a26ab10d37dc80d72e31.jpeg"}],"financialInterests":"No competing interests reported.","formattedTitle":"α-Fe 2 O 3 Tailored Bi 2 WO 6 Hierarchical Microspheres for the Effective Photocatalytic Degradation of Antibiotic Ciprofloxacin and Cationic Rhodamine B Aqueous Dye","fulltext":[{"header":"Highlights","content":"\u003cul class=\"decimal_type\"\u003e\n \u003cli\u003eOne-step hydrothermal route was adopted to synthesize \u0026alpha;-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e heterojunction.\u003c/li\u003e\n \u003cli\u003eRedshift in the absorption spectra by the inclusion of \u0026alpha;-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003epromotes the light harvesting ability of the Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e.\u003c/li\u003e\n \u003cli\u003eBW-Fe-3% heterojunction exhibits excellent photocatalytic efficiency of 98.09% and 97.37% for CIP and RhB degradation.\u003c/li\u003e\n \u003cli\u003eThe plausible photocatalytic degradation mechanism was discussed in detail.\u003c/li\u003e\n\u003c/ul\u003e"},{"header":"1. Introduction","content":"\u003cp\u003eWater is an essential ingredient for sustaining life. The increased use of water in home, agricultural, and industrial sectors has harmed water quality [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e]. Much recent research has revealed that high quantities of emerging pollutants, such as pharmaceutical chemicals, survive in surface waters, soils, and plants. Pharmaceutical compound contamination of water bodies is attributed to two pathways: discharge of medicinal products discharges into water bodies and incorrect discharge of large amounts of medicine left over into the surroundings [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. Greater antibiotic dosages in water sources show that contemporary water management methods are not well appropriate for removing antibiotics from water bodies. Hence, there is tremendous concern, because antibiotics are responsible for antibiotic-resistant bacteria and antibiotic-resistant genes, which can disrupt aquatic systems and endanger human health [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. As a result, numerous strategies for extracting antibiotics from aqueous media have been developed. Notably, when compared to many conventional and advanced oxidation processes (AOPs), \"semiconductor photocatalysis\" has been considered a more realistic choice for antibiotic degradation without the usage of any exogenous supply [\u003cspan additionalcitationids=\"CR5 CR6 CR7\" citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e]. It is a \"green\" technique in which semiconductor-based photocatalysts absorb photons with energy (eV) larger than their bandgap and form a slew of reactive species superoxide (\u0026bull;O\u003csup\u003e2\u003c/sup\u003e\u0026macr;) and hydroxyl (\u0026bull;OH) radicals, and singlet oxygen. TiO\u003csub\u003e2\u003c/sub\u003e has been the maximum preferred semiconductor catalyst for environmental remediation because of its greatest oxidizing power, stability, nontoxicity, and low cost. Nevertheless, TiO\u003csub\u003e2\u003c/sub\u003e's visible light photocatalytic activity is restricted because of its wide range of band gap (3.2 eV). As a result, developing efficient visibly active photocatalysts for pollutant removal is critical [\u003cspan additionalcitationids=\"CR10\" citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]. Because of its strong oxidation potential, visible-light harvesting ability, and non-toxicity, Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e, a layered structure of WO\u003csub\u003e4\u003c/sub\u003e\u003csup\u003e2\u0026minus;\u003c/sup\u003e and Bi\u003csup\u003e2\u003c/sup\u003eO\u003csub\u003e2\u003c/sub\u003e\u003csup\u003e2+\u003c/sup\u003e, demonstrates remarkable photocatalytic properties for the removal of various organic and antibiotic pollutants [\u003cspan additionalcitationids=\"CR13 CR14 CR15 CR16\" citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e has a low quantum efficiency due to the high rate of light-induced electron-hole recombination between the hybrid orbitals of Bi 6s and O 2p, as well as the empty W 5d orbital [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. As a result, effective solutions for suppressing electron and hole recombination are required. The coupling of Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e with a suitable junction has been discovered to be an efficient technique for increasing the efficacy of the photocatalytic activity of the Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e photocatalyst by improving the availability of electrons via effective charge separation.\u003c/p\u003e \u003cp\u003eThe material α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, as an n-type metal oxide with a moderate energy gap between 2.2\u0026ndash;2.4 eV, has been widely researched as a photocatalyst, electrocatalyst, and gas sensor material. Its plentiful raw resources, environmental friendliness, and good conductivity are desirable characteristics for large-scale applications. The unique features of α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e not only increased photocarrier separation and transport but may also result in a higher conduction band level, representing a stronger reduction potential responsible for the formation of reactive species [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. A technique is the combination of α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e semiconductors with appropriate valence (VB) and conduction (CB) band locations favorable for high photocatalytic efficiency. Since, self-assembly of the hierarchical structure constructed with multi nanocrystals as building blocks is an emerging research field in photocatalysis, which provides an available pore wall arrangement and improves electron transport by reducing pressure drop, allowing for more charge carriers to be transferred to the surface of the catalyst, which promotes the improved photoinduced charge separation.\u003c/p\u003e \u003cp\u003eHerein, we report the synthesis of α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e tailored Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e hierarchical microsphere via a simple hydrothermal approach. The α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e heterojunction has significantly improved photocatalytic performance in the removal of ciprofloxacin (CIP) rhodamine B (RhB) within a tailoring dosage of α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e (1\u0026ndash;4%), with Fe-3% exhibiting the best photocatalytic reaction kinetics. The UV-Vis DRS spectra of the heterojunction exhibit an effective redshift from 470 to 550 nm with increasing the modification content of α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e. The photocatalytic mechanism of improved activity was studied and proposed using PL spectra and predicted valence and conduction band positions.\u003c/p\u003e"},{"header":"2. Materials and Methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1 Chemical and Reagents\u003c/h2\u003e \u003cp\u003eBismuth nitrate pentahydrate (Bi(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e.5H\u003csub\u003e2\u003c/sub\u003eO), sodium tungstate dehydrate (Na\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e4\u003c/sub\u003e.2H\u003csub\u003e2\u003c/sub\u003eO), ferric chloride hexahydrate (FeCl\u003csub\u003e3\u003c/sub\u003e.6H\u003csub\u003e2\u003c/sub\u003eO), sodium hydroxide (NaOH), nitric acid (HNO\u003csub\u003e3\u003c/sub\u003e), RhB (C\u003csub\u003e28\u003c/sub\u003eH\u003csub\u003e31\u003c/sub\u003eC\u003csub\u003el\u003c/sub\u003eN\u003csub\u003e2\u003c/sub\u003eO, C.I. 45170) and ciprofloxacin (C\u003csub\u003e17\u003c/sub\u003eH\u003csub\u003e18\u003c/sub\u003eFN\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e) were bought from Sigma-Aldrich, Pvt. Ltd. India. All the materials were of analytical grade (AR) and were utilized further in any purification. Every single experiment was conducted using double-distilled (DD) water.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Synthesis of α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e hierarchical microsphere\u003c/h2\u003e \u003cp\u003eThe hydrothermal process was used to synthesize α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e anchored Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e heterojunction without the aid of any surfactants. Typically, aqueous solutions of FeCl\u003csub\u003e3\u003c/sub\u003e.6H\u003csub\u003e2\u003c/sub\u003eO and NaOH were mixed together to obtain the precipitate of Fe(OH)\u003csub\u003e3\u003c/sub\u003e. The attained product was washed multiple times with DD water and sonicated for 10 min to disperse completely. Then the optimum concentrations of Bi(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e3\u003c/sub\u003e.5H\u003csub\u003e2\u003c/sub\u003eO were added in 30 mL of 1.5 M HNO\u003csub\u003e3\u003c/sub\u003e and sodium tungstate salt was added in 30 mL of distilled water, separately, and mixed with continuous stirring to obtain suspension with white color. After that, different percentages (1, 2, 3, and 4%) of Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e were added whilst being constantly stirred to create the dark red suspension. The resulting mixture was transferred to the 100 mL of Teflon-lined autoclave and the reaction mixture was heated at 160\u0026deg;C for 12 hours. After the autoclave was cooled down to room temperature, the obtained heterojunction powder was collected by centrifugation and washed multiple times with DD water followed by 99% ethanol by centrifugation method and then dried at 70\u0026deg;C. Finally, the obtained α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003eheterojunction with different Fe concentration was labeled as Fe-BW-0%, Fe-BW-1%, Fe-BW-2%, Fe-BW-3% and Fe-BW-4%.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3. Characterizations\u003c/h2\u003e \u003cp\u003eThe powder X-ray diffraction (XRD, PANalytical) method was carried out (Rigaku D/max-RB equipment with Cu K radiation) to examine the purity and crystal structure of the synthesized catalysts. To analyze the morphological structure of the heterojunction, field emission scanning electron microscopy (FE-SEM: JEOL, JSM-5910) followed by transmission electron microscopy (HR-TEM: JEM-2011F, JEOL, Japan) was used. For elemental characterization of the α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003eheterojunction, EDX (EX-2300BU, Jeol) spectroscopic analysis was performed. The elemental mixture and chemical states of the synthesized catalyst were examined using high-resolution X-ray photoelectron spectroscopy (HR-XPS: Leybold-Heraeus LHS-10 spectrometer). A fluorescence spectrophotometer (RF- 5300PC, Shimadzu, Japan) was used to measure the photoluminescence (PL). A UV-visible spectrophotometer equipped with diffused reflectance spectra (Shimadzu UV-2450) was used to examine the absorption spectra of the catalyst.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4. Photocatalytic degradation experiment\u003c/h2\u003e \u003cp\u003eThe photocatalytic activities of all as-prepared photocatalysts were tested by observing the degradation of antibiotic ciprofloxacin and cationic RhB aqueous pollutants when exposed to visible light. A 300 W Xe arc lamp was employed as the light energy source. The following procedure was conducted at room temperature: 20 mg of all synthesized photocatalysts were added separately to 100 mL of 10 ppm ciprofloxacin and rhodamine B aqueous solution. Prior to illumination, the catalyst was dispersed by stirring the suspensions for 30 minutes in the dark. At regular time intervals, 4 mL of the sample was out and the supernatant was collected by centrifugation. The concentration of Ciprofloxacin and RhB aqueous pollutants was determined by determining the absorbance using a UV-Vis spectrophotometer (Shimadzu UV-2450) at maximum absorption of λ\u003csub\u003emax\u003c/sub\u003e at 276 and 554 nm, respectively.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results and Discussion","content":"\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e3.1. Characterizations of synthesized catalysts\u003c/h2\u003e \u003cp\u003e The crystalline structure and purity of Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e and α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e composites were determined using a typical XRD technique. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea, eight distinctive diffraction peaks of pure Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e at 2 theta\u0026thinsp;=\u0026thinsp;28.1, 32.5, 46.4, 56.7, 59.4, 69.4, 76.3, and 78.9\u0026deg; were indexed to the (131), (200), (202), (133), (262), (400), (333), and (204), reflections, indicating that the pure-phase Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e is an orthorhombic structure with the JCPDS Card No. of 79-2381 [\u003cspan additionalcitationids=\"CR23 CR24\" citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. According to Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb, as the Fe/Bi molar ratio was amplified from 1 to 4, the intensity of the diffraction planes matching to the (1 1 0) of α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e (JCPDS 33\u0026ndash;0664) steadily rose, implying that the α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e was formed in the α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e heterojunction [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]. In the patterns, no recognizable peaks of any impurity were found. As a result, the hierarchically structured composite comprises Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e and α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e2\u003c/span\u003e (a and b) SEM images of Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e, (c) lattice fringes of Fe-BW-3%, mapping analysis images of (d) mixed, (e) Bi, (f) W, (g) O and (h) Fe, (i) EDAX spectrum of Fe-BW-3% catalyst.\u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e2\u003c/span\u003e shows SEM and HR-TEM images of the Fe-BW-3 catalyst. The SEM image in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e2\u003c/span\u003ea indicates that the Fe-BW-3 catalyst is a homogenous, sphere-like hierarchically built structure ranging in diameter from 2 to 5 um. The microsphere was generated by self-assembling and Ostwald ripening smooth nanoplates. Because of the vast number of pores in the overlapping nanosheets, Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e can be employed as a transmission mechanism for tiny molecules. It aided the reactant and product molecules by moving into and out of the substance and facilitating chemical reactions. The interplanar spacing computed from the lattice fringes was 209 nm, which corresponds to the (131) plane of the orthorhombic Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e structure. Furthermore, elemental mapping and EDS were employed to evaluate the Fe-BW-3% catalyst; the results proved the presence of the components Bi, W, Fe, and O, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e2\u003c/span\u003ei [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e2\u003c/span\u003ed-h, the elemental mapping images demonstrated that Bi, W, Fe, and O were spread uniformly.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe presence and chemical state of the elements in the α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e heterojunction were analyzed through high-resolution HR-XPS spectra. The doublet signals correspond to the Bi 4f\u003csub\u003e5/2\u003c/sub\u003e and 4f\u003csub\u003e3/2\u003c/sub\u003e signals were perceived at binding energies (BE) of 164.4 eV and 159.1 eV, respectively, which could be allocated to the Bi\u003csup\u003e3+\u003c/sup\u003e species in the sample (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e3\u003c/span\u003ea) [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]. The W 4f\u003csub\u003e7/2\u003c/sub\u003e and 4f\u003csub\u003e5/2\u003c/sub\u003e were consigned two distinctive signals in the W 4f spectra at 37.54 eV and 35.36 eV, respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e3\u003c/span\u003eb)[\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]. The signal at 725 eV belonged to Fe 2p\u003csub\u003e1/2\u003c/sub\u003e, as shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e3\u003c/span\u003ec, indicating the existence of Fe\u003csup\u003e3+\u003c/sup\u003e. Also, the O 1s core level spectra exhibited a significant signal at 530.1 eV, which corresponds to lattice oxygen. The XPS examination results show the creation of α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e in the α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e heterojunction, which is consistent with the powder XRD analysis.\u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003ea depicts the UV-visible diffuse reflection spectra (DRS) of Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e, Fe-BW-1%, Fe-BW-2%, Fe-BW-3%, and Fe-BW-1%. Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e exhibits absorption in the UV to visible region with a shorter wavelength than 460 nm. The spectrum's crisp shape suggests that the visible-light absorption was generated by the band-gap transition instead of the transition from the impure conduct level. The optical absorption of α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e composite exhibits a significant shift towards higher wavelength and enhanced absorbance in the visible-light region when compared to pure Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e, which can be attributed to the communal photosensitization of Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e and α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e. Furthermore, the increased loading of α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e in the composite appears to improve visible light absorption. It demonstrates that modifying α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e can effectively extend the visible-light responsiveness of Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e, which is advantageous to using direct sunlight energy for the degradation of pollutants.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe photoluminescence (PL) spectra of the catalyst resulting from the rate of the electron-hole recombination can be utilized to reveal the electron movement, transfer, and recombination mechanisms of photoinduced electrons with holes [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e]. The reduced PL intensity frequently suggests a reduced recombination rate and, as a result, enhanced photocatalytic activity. Figure\u0026nbsp;\u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003eb depicts recorded PL spectra of bare Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e and α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e heterojunction stimulated at 320 nm with varying Fe percentages, which also had the same broad emission in the 400\u0026ndash;550 nm range. However, the PL intensities of the heterojunction catalysts are reduced, indicating that a heterojunction effect has been produced between α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e. The composite containing Fe-3% had the smallest PL emission, indicating the greatest hindrance to photogenerated carrier recombination. However, the PL emission of heterojunction with Fe-4% increases when compared to composite with Fe-3%. Under light illumination, the BW-Fe-3% catalysts were found to have higher activity in the removal of antibiotic ciprofloxacin and cationic rhodamine B aqueous dye.\u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e UV-Vis DRS and photoluminescence spectra of Fe-BW-0%, Fe-BW-1%, Fe-BW-2%, Fe-BW-3% and Fe-BW-4% catalysts\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e3.2 Photocatalytic degradation activity\u003c/h2\u003e \u003cp\u003eCiprofloxacin and rhodamine B were chosen as pharmaceutical and cationic dye pollutants to assess the photocatalytic capacity of all synthesized photocatalysts. The CIP and RhB degradation efficiency for all synthesized materials studied and shown in Figs.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea-d and \u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea-d was calculated, as was the seeming rate constant (k) based on a pseudo-first-order kinetic technique. In the absence of a photocatalyst, the degradation efficiency was minimal in the dark reaction, indicating that the CIP (1.97%) and RhB (2.3%) were primarily degraded by catalyst photo-absorption. In addition, the dark test was conducted for the adsorption of pollutants (CIP and RhB) removal, with the percentages being 13.33 and 21.68%, respectively (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003eb and \u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003eb). Pristine Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e demonstrated minimal photocatalytic activity for CIP (42.4%) and RhB (56.8%) after 180 min. of visible light irradiation. CIP and RhB removal effectiveness was significantly improved over α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003eheterojunction and the corresponding absorption plots were presented \u003cb\u003ein\u003c/b\u003e Figs.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ea and \u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ea. Among all samples, the BW-Fe-3% catalyst demonstrated the highest photocatalytic efficiency of 98.09% and 97.37% for CIP and RhB degradation, respectively. CIP and RhB degradation percentages for BW-Fe-1%, BW-Fe-2%, and BW-Fe-4% were calculated to be 49.71 and 68.8%, 70.35 and 76.84%, and 88.67 and 88.25%, respectively. The kinetic model (k= -ln(C\u003csub\u003et\u003c/sub\u003e/C\u003csub\u003e0\u003c/sub\u003e)) was utilized to evaluate the dye removal kinetics, as shown in Figs.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003ed and \u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003ed. The kinetic values of CIP degradation for BW, BW-Fe-1%, BW-Fe-2%, BW-Fe-3%, and BW-Fe-4%, respectively, were estimated to be 0.00329, 0.0054, 0.00259, 0.01843, and 0.01066 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively. Also, the kinetic values of 0.0066, 0.00448, 0.00761, 0.01953, and 0.01169 min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e were obtained for RhB degradation using BW, BW-Fe-1%, BW-Fe-2%, BW-Fe-3%, and BW-Fe-4% catalysts. The increased photocatalytic degradation efficiency is principally owing to the considerable amount of visible light harvested and the decreased rate of photoinduced electron-hole recombination caused by α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e-tailored Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e heterojunction formation.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThe peak shift for RhB deterioration has been observed towards the lower wavelength. RhB is well known for its capability to harvest visible light (480\u0026ndash;580 nm) range due to the dye's ground and excited states. The energy potential of the conduction band of Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e is negative than the lowest empty molecular orbit of RhB. As a result, the photosensitized process, which involves transferring an excited electron from RhB to Bi2WO6's conduction band, is thermodynamically possible. The blue shift has been identified as a stepwise N-de-ethylation of RhB caused by photosensitization. According to the findings, RhB degradation is caused by the interaction of band cleavage degradation of connected structures and photosensitized N-de-ethylation processes.\u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e (a) Absorption spectra of CIP degradation over Fe-BW-3% catalyst, % of degradation, C\u003csub\u003et\u003c/sub\u003e/C\u003csub\u003e0\u003c/sub\u003e and \u0026ndash;ln(C\u003csub\u003et\u003c/sub\u003e/C\u003csub\u003e0\u003c/sub\u003e) for Fe-BW-0%, Fe-BW-1%, Fe-BW-2%, Fe-BW-3% and Fe-BW-4% catalysts\u003c/p\u003e \u003cp\u003e The recycling experiments in the light-irradiated photocatalytic degradation of both CIP and RhB were tested to assess the stability of the best-performing (BW-Fe-3%) photocatalyst, which is a significant consideration in practical use. The photocatalyst does not show the apparent loss in photocatalytic degradation of both CIP and RhB after six repeated cycles, as illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003ea. BW-Fe-3% composite is thought to have potential applications for lowering water pollutants due to its outstanding photocatalytic performance and good reusability.\u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e(a) Absorption spectra of RhB degradation over Fe-BW-3% catalyst, % of degradation, C\u003csub\u003et\u003c/sub\u003e/C\u003csub\u003e0\u003c/sub\u003e and \u0026ndash;ln(C\u003csub\u003et\u003c/sub\u003e/C\u003csub\u003e0\u003c/sub\u003e) for Fe-BW-0%, Fe-BW-1%, Fe-BW-2%, Fe-BW-3% and Fe-BW-4% catalysts\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003e3.3. Photocatalytic degradation mechanism\u003c/h2\u003e \u003cp\u003eScavenging experiments were carried out prior to the mechanism to recognize the primary reactive species for the degradation of CIP and RhB [\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e, \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e]. IPA was utilized as a \u0026bull;OH scavenger, KI as a h\u003csup\u003e+\u003c/sup\u003e radicals scavenger, CCl\u003csub\u003e4\u003c/sub\u003e as an electron scavenger, and BQ as a superoxide radicals scavenger. For CIP photodegradation, superoxide, electrons, hydroxyl, and holes group degradation rates were 10.34, 6.43, 40.63, and 69.43%, respectively. Similarly, RhB degradation studies with superoxide, electrons, hydroxyl, and hole groups were carried out, and the percentages obtained were 7.53, 3.53, 30.43, and 74.55%, respectively. The results indicated that the addition of BQ and CCl\u003csub\u003e4\u003c/sub\u003e to the reaction had no significant effect. This revealed that the principal active species in the photocatalytic reaction were not free electrons and \u0026bull;O\u003csup\u003e2\u0026minus;\u003c/sup\u003e radicals. The reaction was greatly hindered when KI was introduced, representing that the primary reactive species were holes and hydroxyl radicals were identified as the secondary active radicals.\u003c/p\u003e \u003cp\u003eTheoretical prediction using absolute electronegativity is an efficacious method for determining the band edge of oxide photocatalysts. The following calculation can be used to compute a semiconductor's valence and conduction band edge at zero charge[\u003cspan additionalcitationids=\"CR35\" citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e]:\u003cdiv id=\"Equa\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e\n$${E}_{CB}=X-{E}_{0}-0.5{E}_{g}$$\u003c/div\u003e\u003c/div\u003e\u003cdiv id=\"Equb\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equb\" name=\"EquationSource\"\u003e\n$${E}_{VB}={E}_{CB}+{E}_{g}$$\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eWhere X denotes the electronegativity of a metal oxide, given as the mean values of presented atoms in the catalysts; E\u003csub\u003ec\u003c/sub\u003e denotes the energy of free electrons related to the hydrogen scale (about 4.5 eV); E\u003csub\u003eg\u003c/sub\u003e denotes the semiconductor's energy bandgap. Based on the calculated E\u003csub\u003eg\u003c/sub\u003e of Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e in UV-Vis absorption. The CB and VB locations of Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e are both more anodic than α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e catalyst. As a result, the band-gap potential difference would cause irreversible carrier transfer at the α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e interface.\u003c/p\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e Probable photocatalytic mechanism for the removal of CIP and RhB over α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e tailored Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003eheterojunction.\u003c/p\u003e \u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e, under Xe lamp irradiation, Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e and α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e can be concurrently induced to excite electrons from the VB to the CB and holes left in the semiconductor valence band. Following that the e\u0026macr; from the CB of α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e would be swiftly transferred to the conduction band of Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e, while h\u003csup\u003e+\u003c/sup\u003e from the VB of Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e may be transported to that of α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e. Therefore, the photoinduced electrons and holes are effectually segregated at the α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e interface before migrating to the surfaces of structures to be involved in the photocatalytic degradation process. The enhanced photocatalytic activity for CIP photodegradation can be ascribed to the synergy effect of α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e. With the photocatalytic and photosensitized processes collaborate to degrade RhB dye. Rhodamine b can absorb incident light flux due to the intermolecular transition, in addition to the energy bandgap coupling of semiconductors. The excited state photoelectrons can be directly transferred into the CB of Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e and subsequently caught by O\u003csub\u003e2\u003c/sub\u003e to initiate further processes for dye mineralization. As a result, the α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e composite has improved photodegradation efficacy for both dye and antibiotic contaminants.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"4. Conclusion","content":"\u003cp\u003eThe hierarchically α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003eheterojunction was effectively synthesized in a facile hydrothermal technique and characterized well. The diffused reflectance spectroscopy of the α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e heterojunction revealed a red shift when compared to bare Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e. The photocatalytic performance of the BW-Fe heterojunction photocatalyst in the removal of CIP and RhB aqueous pollutants under light illumination was significantly greater than that of pristine Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e. The improved photocatalytic performance of the α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e/Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e composite can be ascribed to its hierarchical enhanced photo absorption and effective charge carrier separation. After six reaction cycles, the heterojunction catalyst still showed strong photocatalytic activity for both CIP and RhB degradation. Thus, the combination of Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e and α-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e will be attractive since it may exist as a means to endorse the charge separation of photoinduced electrons and holes and boost photocatalytic efficiencies for the removal of antibiotic and cationic dye pollutants.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eConflict of Interest statement:\u0026nbsp;\u003c/strong\u003eThis research did not involve human or animal samples.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData Availability Statement:\u003c/strong\u003e Applicable based on request\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgement:\u0026nbsp;\u003c/strong\u003eDr. Mohd Afzal extends his appreciation to Researchers Supporting Project number (RSPD2024R979), King Saud University, Riyadh, Saudi Arabia, for financial assistance.\u0026nbsp;\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eStatements \u0026amp; Declarations\u003c/strong\u003e We confirm that the manuscript has been read and approved by all named authors and that there are no other persons who satisfied the criteria for authorship but are not listed. 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Alloys Compd. 662 (2016) 598\u0026ndash;606. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1016/j.jallcom.2015.12.050\u003c/span\u003e\u003cspan address=\"10.1016/j.jallcom.2015.12.050\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e.\u003c/span\u003e\u003c/li\u003e \u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Bi2WO6, α-Fe2O3, Photocatalysis, ciprofloxacin, Rhodamine B","lastPublishedDoi":"10.21203/rs.3.rs-3888631/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3888631/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eα-Fe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e tailored Bi\u003csub\u003e2\u003c/sub\u003eWO\u003csub\u003e6\u003c/sub\u003e hierarchical microspheres have been effectively synthesized and well characterized. The photocatalytic efficacy was improved by the Fe-BW-3% heterojunction on the degradation of ciprofloxacin as a pharmaceutical and rhodamine B as a cationic dye pollutant. The increased photocatalytic activity was attributed to the increment of visible light absorbing ability and reduced rate of light-induced electron and hole recombination by moving electrons from one junction to another. The recycle investigations revealed that the catalysts are stable for CIP and RhB degradation after six cycles. Furthermore, scavenging experiments show that holes were the primary active species for the CIP and RhB degradation.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e","manuscriptTitle":"α-Fe 2 O 3 Tailored Bi 2 WO 6 Hierarchical Microspheres for the Effective Photocatalytic Degradation of Antibiotic Ciprofloxacin and Cationic Rhodamine B Aqueous Dye","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-01-29 16:27:30","doi":"10.21203/rs.3.rs-3888631/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"64ea79f8-ca76-4a37-8d3b-5939e3562163","owner":[],"postedDate":"January 29th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2024-02-07T22:46:57+00:00","versionOfRecord":[],"versionCreatedAt":"2024-01-29 16:27:30","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-3888631","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3888631","identity":"rs-3888631","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}